JP4170827B2 - Polycarbonate resin composition - Google Patents

Description

（式中、Ｒ³としては、それぞれ独立に、水素原子、炭素数１〜３０のアルキル基、炭素数６から５０のアリール基、アリールアルキル基、ポリエーテルの基、ポリオルガノシロキサンの基を示す。）
【００２２】
該Ｒ³におけるアルキル基、アリール基、アリールアルキル基としては、前に例示したような基があげられるが、好ましくは、メチル基、エチル基、プロピル基、ブチル基、フェニル基等が挙げられる。
また、ポリエーテルの基としては、ジオールや環状エーテルから誘導される基であれば、脂肪族、芳香族のいずれでもよいが、好ましくは、エチレングリコール、エチレンオキサイド、プロピレングリコール、プロピレンオキサイドから誘導される基が好ましく、繰り返し単位の数としては、１〜１００、好ましくは２〜１００であり、又、その末端はＯＨ構造でもアルキルエーテル構造でも良い。ポリオルガノシロキサンの基としては、繰り返し単位が３〜１０００であり、好ましい下限は６であり、上限は１００であり、さらに好ましくは５０である。ポリオルガノシロキサンの基としては、炭素数１〜３０のアルキル基や、炭素数６〜５０のアリール基やアリールアルキル基を有するポリオルガノシロキサンの基であるのが好ましい。
【００２３】
本発明で使用するシロキサン化合物としては、シロキサン結合が直鎖状に連結した構造のものが好ましいが、一部に分岐構造を有していてもよい。そして本発明では、直鎖状のシロキサン化合物の側鎖に、上述したような、少なくとも１つずつの（１）芳香族炭化水素基、（２）カルボン酸エステル結合及び／又はエーテル結合を少なくとも１個有する脂肪族もしくは芳香族の有機基、及び（３）リン原子含有基を結合してなるものがより好ましく使用される。
【００２４】
該直鎖状のポリオルガノシロキサンとしては、Ｍ−(Ｗ)_n−Ｍで示される構造のものが挙げられる。
（Ｍは一官能性構造単位を示し、Ｗは二官能性構造単位を示し、ｎは３〜１，０００の整数を示す。Ｗは、脂肪族系構造単位（Ａ）、芳香族系構造単位（Ｂ）、カルボン酸エステル結合及び／又はエーテル結合を有する構造単位（Ｃ）、リン原子含有構造単位（Ｄ）からなり、該Ｗを１としたとき、該Ｗを構成する各構造単位の割合が、それぞれＡ＝０〜０．６、Ｂ＝０．１〜０．９、Ｃ＝０．０１〜０．４、Ｄ＝０．０１〜０．４である。）
【００２５】
Ｍの具体例としては、たとえば、
【００２６】
【化４】

（式中、Ｒはそれぞれ独立に脂肪族炭化水素基を表す）
で示される構造の基が挙げられる。さらに具体的には、該式中のＲとして、炭素数１〜１０のアルキル基などが好ましい。例えば、
【００２７】
【化５】

【００２８】
等の基が挙げられるが、これに限定されない。
さらに本発明で使用するオルガノシロキサンは、下記構造式（II）で示されるような構造のものが好ましい。
【００２９】
【化６】

【００３０】
（式中、Ｒは、脂肪族炭化水素基を表し、Ｘは水素原子、脂肪族炭化水素基、または芳香族炭化水素基であって、ただし、少なくとも一方が芳香族炭化水素基を表し、Ｙは水素原子、脂肪族炭化水素基、芳香族炭化水素基、またはカルボン酸エステル結合及び／又はエーテル結合を少なくとも一個有する脂肪族もしくは芳香族の有機基であって、ただし、少なくとも一方が該有機基であり、Ｚは水素原子、脂肪族炭化水素基、芳香族炭化水素基、またはリン原子含有基であって、ただし、少なくとも一方がリン原子含有基であり、さらに３≦ａ＋ｂ＋ｃ＋ｄ≦１０００であり、かつａは０以上の整数、ｂ、ｃ及びｄはそれぞれ正の整数を表す。）
【００３１】
該構造式(II)において、前記Ｍ−(Ｗ)_n−Ｍの式中で、Ｗの二官能性基に相当する部分としての、脂肪族系構造単位（Ａ）、芳香族系構造単位（Ｂ）、カルボン酸エステル結合及び／又はエーテル結合を有する構造単位（Ｃ）、リン原子含有構造単位（Ｄ）は、それぞれ以下の通りであり、本発明で使用するポリオルガノシロキサンとしては、これらの構成単位ＡからＤが、それぞれ以下のものから選ばれる化合物が好ましいものとして挙げられる。なお、以下の各構成単位の具体例においては、１単位のみの場合（すなわち、ａ，ｂ，ｃ，ｄがそれぞれ１の場合）を示した。
【００３２】
【化７】

【００３３】
構成単位Ａの具体例
【００３４】
【化８】

【００３５】
構成単位Ｂの具体例
【００３６】
【化９】

【００３７】
構造単位Ｃの具体例
【００３８】
【化１０】

【００３９】
構造単位Ｄの具体例
【００４０】
【化１１】

【００４１】
また、各構成単位のａ，ｂ，ｃ，ｄは、これら構成単位の、構成数を示すものであり、ａは０を以上の整数、ｂ、ｃ及びｄはそれぞれ正の整数を表す。好ましくはａ＋ｂ＋ｃ＋ｄの下限は３であり、上限は１０００である。ａ＋ｂ＋ｃ＋ｄが、３未満であると、揮散性等の問題があり、好ましくない。より好ましい下限は６である。また上限は、好ましくは１００以下であり、より好ましくは５０以下である。余り大きすぎると粘度が高くなり過ぎ、ハンドリング性が悪くなる。ａ，ｂ，ｃ，ｄを全二官能性構成単位（Ｗ）の数に対する割合で表現した値を各々Ａ，Ｂ，Ｃ，Ｄと表現する。
Ａの下限は、好ましくは０であり、上限は、好ましくは０．６である。Ａが、０．６を超えると、透明性に影響を及ぼすので好ましくない。
【００４２】
Ｂの下限は、好ましくは０．１であり、上限は、好ましくは０．９である。Ｂが０．１未満では、透明性に問題があるため好ましくなく、又、０．９を超える場合は、流動性改良効果に劣るため好ましくない。Ｂのより好ましい下限は、０．２である。又、より好ましい上限は、０．８５である。
【００４３】
Ｃの下限は、好ましくは０．０１であり、上限が、好ましくは０．４である。Ｃが０．０１未満であると透明性が劣るため好ましくなく、０．４を超えると耐熱性に劣るため、好ましくない。Ｃのより好ましい下限は、０．０５である。又、より好ましい上限は、０．３である。
Ｄの下限は、好ましくは０．０１であり、上限は、好ましくは０．４である。Ｄが０．０１未満であると、流動性改良効果に劣り、０．４を超えると耐熱性に劣るため好ましくない。Ｄの好ましい下限は、０．０５である。又、より好ましい上限は、０．３である。
なお、これらの構造単位の比率は、シロキサン化合物を、¹Ｈ−ＮＭＲで分析した測定データから算出してモル含有率（ｍｏｌ／ｍｏｌ）で示したものである。
【００４４】
本発明で使用するシロキサン化合物は、上述の特徴を有するものであり、これらは単独で使用しても、二種類以上混合して使用しても良い。
【００４５】
また、該シロキサン化合物は、公知の方法により得ることが出来、例えば、シリコーンハンドブック（日刊工業新聞社（１９９０））に詳述されている。
具体的には、置換法や直接法により、オルガノクロロシランを合成し、更にアルコールなどを反応させて、オルガノアルコキシシラン等を得る。これらオルガノクロロシランやオルガノアルコキシシランを用いて縮合反応によりシロキサン化合物が得られる。この様にして得られるシロキサン化合物中のＳｉ−Ｈ基に、目的のシロキサン化合物の置換基に対応する、アルケン、アルキン、アルコール、カルボン酸、リン酸等の各種官能基を含有する化合物を付加反応させることにより、得ることが出来る。このＳｉ−Ｈ基の付加反応に際して、触媒として、白金、パラジウム、ニッケル、ロジウム等の金属或いはそれらの化合物や錯体等を用いて行っても良い。本発明で使用するシロキサン化合物は、例えば特開平６−１２８３８０号公報に記載のオルガノポリシロキサン−ポリラクトン共重合体の製造方法や、特開２００１−２４７５８２号公報に記載のリン酸化ポリオルガノシロキサンの製造方法等を適用することができる。
また、このようなシロキサン化合物を市場より入手してもよい。
【００４６】
本発明の熱可塑性樹脂組成物に於けるポリカーボネート樹脂とシロキサン化合物の割合は、ポリカーボネート樹脂１００重量部に対し、シロキサン化合物０．００１〜２０重量部の範囲である。シロキサン化合物が０．００１重量部未満では流動性改良効果が不十分であり、２０重量部を超えると耐熱性が不十分となる。シロキサン化合物の割合の下限は、好ましくは０．０５重量部以上であり、より好ましくは０．１重量部以上である。シロキサン化合物の割合の上限は、好ましくは１０重量部以下であり、より好ましくは５重量部以下である。
【００４７】
本発明のポリカーボネート樹脂組成物は、流動性と透明性の両方に優れており、ＪＩＳ Ｋ６７１４に基づき測定したヘーズ（試験片肉厚３ｍｍ）が１０％以下である場合に、有用である。５％以下である場合には特に有用である。
本発明の熱可塑性樹脂組成物を製造する方法としては、最終成形品を成形する直前までの任意の段階で、当業者に周知の種々の方法によって配合し、混練する方法が挙げられる。配合方法としては、例えば、タンブラー、ヘンシェルミキサー等で混合する方法や、フィーダーにより定量的に押出機ホッパーに供給して混合する方法等が挙げられる。混練方法としては、一軸押出機、二軸押出機などを用いて混練する方法が挙げられる。
【００４８】
本発明の熱可塑性樹脂組成物には更にその目的に応じ、所望の特性を付与する為のポリエステル系樹脂、ポリスチレン系樹脂、ポリオレフィン系樹脂等の他のポリマーや、難燃剤、耐衝撃改良剤、酸化防止剤、熱安定剤、紫外線吸収剤、帯電防止剤、可塑剤、離型剤、滑剤、相溶化剤、発泡剤、ガラス繊維、ガラスビーズ、ガラスフレーク、炭素繊維、繊維状マグネシウム、チタン酸カリウムウィスカー、セラミックスウィスカー、マイカ、タルク等の補強剤、充填剤、染顔料等を、一種又は二種以上添加含有させてもよい。
【００４９】
本発明の熱可塑性樹脂組成物は、射出成形、ブロー成形等、慣用の成形方法に従って、所望の成形品とすることができる。本発明の熱可塑性樹脂組成物からなる成型品の用途としては、例えば、シート、フィルム、雑貨、家電部品、自動車部品、建築材料、中空容器などが挙げられる。
【００５０】
【実施例】
以下、本発明を実施例により更に詳細に説明するが、本発明はその要旨を超えない限り、以下の実施例に限定されるものではない。
各実施例にて使用した原材料は下記の通りである。
（１）ポリカーボネート樹脂：三菱エンジニアリングプラスチックス株式会社製品 商品名：ユーピロン Ｓ−２０００（粘度平均分子量２５，０００）
（２）ポリカーボネート樹脂：三菱エンジニアリングプラスチックス株式会社製品 商品名：ユーピロン Ｈ−３０００（粘度平均分子量１９，０００）
（３）ポリカーボネート樹脂：三菱エンジニアリングプラスチックス株式会社製品 商品名：ユーピロン Ｅ−２０００（粘度平均分子量２７，０００）
（４）ポリカーボネート樹脂：三菱エンジニアリングプラスチックス株式会社製品 商品名：ユーピロン Ｈ−４０００（粘度平均分子量１５，０００）
（５）〜（１９）シロキサン化合物Ａ〜Ｎ，Ｑ：日本ユニカー株式会社製（下記表１記載）
（２０）シロキサン化合物Ｏ：ポリジメチルシロキサン：日本ユニカー株式会社製品 商品名：Ｌ−４５
（２１）シロキサン化合物Ｐ：メチルトリメトキシシラン：日本ユニカー株式会社製品 商品名：Ａ−１６３
（２２）ＰＣＬ：ダイセル化学工業株式会社製 商品名：プラクセル Ｈ１Ｐ（ポリカプロラクトン；分子量１０，０００
なお、表中の構造単位の比率は、シロキサン化合物を、1Ｈ−ＮＭＲで分析した測定データから算出してモル含有率（ｍｏｌ／ｍｏｌ）で示し、粘度は５０℃における測定値を示した。
【００５１】
【表１】

【００５２】
なお、表１中の置換基を示すＡ−１、Ｂ−１、Ｂ−２，Ｃ−１ａ、Ｃ−１ｂ、Ｃ−２ａ、Ｃ−２ｂ、Ｃ−２ｃ、Ｄ−１、Ｄ−２、Ｄ−３は、それぞれ以下のような置換基を示す。
【００５３】
【化１２】

【００５４】
【化１３】

【００５５】
〔実施例１〜１７〕〔比較例１〜１２〕
表２、表３に記載の比率で、ポリカーボネート樹脂と同表に記載のシロキサン化合物、またはＰＣＬとを、ヘンシェルミキサー、又はタンブラーにて混合し、φ６５ｍｍの一軸ベント式押出機を用いて、バレル温度２７０℃で押出してペレットを得た。このペレットを熱風乾燥器中で１２０℃にて５時間以上乾燥した後、樹脂温度２８０℃、金型温度８０℃にて、物性測定用試験片を射出成形し、評価を行った。結果を表２、表３に示す。
【００５６】
【表２】

【表３】

【００５７】
〔実施例１８〕〔比較例１３〕
表４に記載の比率で、ポリカーボネート樹脂に、同表に記載のシロキサン化合物Ａを添加した場合（実施例１８）と、添加しない場合（比較例１３）の配合とし、ヘンシェルミキサー、又はタンブラーにて混合し、φ６５ｍｍの一軸ベント式押出機を用いて、バレル温度２７０℃で押出してペレットを得た。このペレットを熱風乾燥器中で１２０℃にて５時間以上乾燥した後、樹脂温度２８０℃、金型温度８０℃にて、物性測定用試験片を射出成形し、評価を行った。結果を表４に示す。
【００５８】
【表４】

【００５９】
〔実施例１９〜２３〕
表５に記載の比率で、ポリカーボネートと樹脂と同表に記載のシロキサン化合物とを、ヘンシェルミキサー、又はタンブラーにて混合し、φ６５ｍｍの一軸ベント式押出機を用いて、バレル温度２７０℃で押出してペレットを得た。このペレットを熱風乾燥器中で１２０℃にて５時間以上乾燥した後、樹脂温度２８０℃、金型温度８０℃にて、物性測定用試験片を射出成形し、評価を行った。結果を表５に示す。
【００６０】
【表５】

【００６１】
各実施例における評価方法は下記の通りである。
透明性（Ｈａｚｅ）：ＪＩＳ Ｋ６７１４に基づき、厚さ３ｍｍの試験片を用いて、ヘーズを測定した。
流動性（Ｑ値）（ｃｃ／ｓ）：高化式フローテスターを用いて、荷重１６０ｋｇｆ／ｃｍ²、直径１ｍｍ×長さ１０ｍｍのノズルからの２８０℃における、樹脂の流出量を測定した。
引張強度（ＭＰａ）：ＡＳＴＭ Ｄ６３８に基づき、２３℃にて測定した。
荷重撓み温度（ＤＴＵＬ）：ＡＳＴＭ Ｄ−６４８に基づき、荷重１．８２ＭＰａにて測定した。
ＢＦ長（ｍｍ）：厚さ２ｍｍのバーフロー金型を用い、樹脂温度２８０℃、金型温度８０℃、射出圧力１５００ｋｇｆ／ｃｍ²、成形サイクル４５秒の条件で成形を行い、試料１５点のバーフロー長の平均値にて評価した。この数値が大きい程流動性が良いことを表す。
耐衝撃性（Ｉｚｏｄ衝撃強度（Ｊ／ｍ））：ＡＳＴＭ Ｄ２５６に基づき、厚さ３．２ｍｍの試験片を用いて、ノッチ付きアイゾッド法にて測定した。
【００６２】
【発明の効果】
本発明の熱可塑性樹脂組成物は、流動性がポリカーボネート樹脂に比べ非常に優れており、ヘーズの値が小さく透明性に優れており、しかも耐熱性や耐衝撃性も良好であり、透明性を要し、且つ流動性、耐熱性及び耐衝撃性が必要な各種用途に有用である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a polycarbonate resin composition, and more particularly, to a polycarbonate resin composition excellent in transparency and fluidity comprising a polycarbonate resin and a siloxane compound.
[0002]
[Prior art]
Thermoplastic resins, particularly polycarbonate resins, are used in a wide range of applications because they have excellent mechanical strength, impact strength, heat resistance, electrical properties, transparency, and the like. However, in general, since the melting temperature is high and the viscosity at the time of melting is high, the moldability is poor.
[0003]
For this reason, it is generally known that the flowability can be improved by lowering the molecular weight of the polycarbonate resin, but at the same time, there is a problem that the mechanical properties, particularly the impact resistance is lowered.
[0004]
Therefore, conventionally, attempts have been made to blend various plasticizers and various resins in order to improve the fluidity of the polycarbonate resin.
[0005]
For example, a method of blending a cyclic siloxane compound is disclosed in JP-A-55-18406, a method of blending a siloxy-oxyalkylene block copolymer is disclosed in JP-A-54-100453, and a silicone chain is copolymerized with polycarbonate. JP-A-3-79626 discloses a method using polydimethylsiloxane-added isopropenylphenol as a polycarbonate chain terminator. JP-A-3-84028 discloses a method of reacting an epoxy group organosiloxane with a polycarbonate at both ends. Various methods such as those described in Japanese Patent No. 3090764 have been proposed, but all of them are insufficient in effect, or sacrifices transparency, mechanical properties, heat resistance, etc. And expensive, each has a problem.
[0006]
[Problems to be solved by the invention]
The objective of this invention is providing the polycarbonate resin composition excellent in transparency and fluidity | liquidity.
[0007]
[Means for Solving the Problems]
The present invention has been made in order to solve the above-mentioned problems, and the gist thereof includes (B) siloxane compound 0.001 to 20 parts by weight with respect to (A) 100 parts by weight of the polycarbonate resin. In the polycarbonate resin composition, the siloxane compound of component (B) has at least one (1) aromatic hydrocarbon group, (2) carboxylic acid ester bond and / or ether bond on the silicon atom in the structure. The present invention relates to a polycarbonate resin composition, which is a polyorganosiloxane formed by bonding an aliphatic or aromatic organic group and (3) a phosphorus atom-containing group.
[0008]
Hereinafter, the present invention will be described in detail.
The polycarbonate resin in the present invention can be obtained by a known method, for example, detailed in a polycarbonate resin handbook (Nikkan Kogyo Shimbun Co., Ltd. (1992)), and includes interfacial polymerization, pyridine, and transesterification. Various manufacturing methods including the above are mentioned.
Specifically, an aromatic dihydroxy compound or a small amount thereof and a polyhydroxy compound, carbonyl chloride generally known as phosgene, or a carbonic acid diester represented by dimethyl carbonate or diphenyl carbonate, or carbon monoxide or carbon dioxide It is a polymer or copolymer of a linear or branched thermoplastic aromatic polycarbonate obtained by reacting with the carbonyl compound.
[0009]
As aromatic dihydroxy compounds, 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A), 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane (= tetrabromobisphenol A) Bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, 2 , 2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethyl) Phenyl) propane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro) -4-hydroxyphenyl) propane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 1,1-bis (4- Hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane, 2,2-bis (4-hydroxyphenyl) -1,1,1-trichloropropane, 2,2-bis (4-hydroxyphenyl) Bis (1) exemplified by -1,1,1,3,3,3-hexachloropropane, 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, etc. Hydroxyaryl) alkanes; 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) silane Bis (hydroxyaryl) cycloalkanes exemplified by rhohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and the like; 9,9-bis (4-hydroxyphenyl) fluorene, Cardo structure-containing bisphenols exemplified by 9,9-bis (4-hydroxy-3-methylphenyl) fluorene; 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dimethyldiphenyl ether, etc. Dihydroxy diaryl ethers, such as 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide, etc .; 4,4′-dihydroxydiphenyl Sulfoxide, 4,4'-dihydroxy Dihydroxydiaryl sulfoxides exemplified by -3,3'-dimethyldiphenyl sulfoxide and the like; dihydroxydiaryls exemplified by 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfone and the like Sulfones; hydroquinone, resorcin, 4,4′-dihydroxydiphenyl and the like. These aromatic dihydroxy compounds may be used alone or in admixture of two or more. Among these, 2,2-bis (4-hydroxyphenyl) propane is particularly preferably used.
[0010]
In order to obtain a branched aromatic polycarbonate resin, phloroglysin, 2,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) -3-heptene, 4,6-dimethyl-2,4, 6-tris (4-hydroxyphenyl) -2-heptene, 1,3,5-tris (2-hydroxyphenyl) benzol, 1,1,1-tris (4-hydroxyphenyl) ethane, 2,6-bis ( Polyhydroxy compounds exemplified by 2-hydroxy-5-methylbenzyl) -4-methylphenol, α, α ′, α ″ -tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene, and the like, or 3,3-bis (4-hydroxyaryl) oxindole (= isatin bisphenol), 5-chlorisatin bisphenol, 5,7-dichloro Satin bisphenol, 5-bromoisatin bisphenol, or the like may be used.
[0011]
In the case of an interfacial polymerization polycarbonate, a terminal terminator or a molecular weight modifier may be used. Examples of the terminal terminator or molecular weight regulator include a monovalent phenolic hydroxyl group or a compound having a monovalent carboxylic acid derivative structure. Examples of the compound having a monovalent phenolic hydroxyl group include substituted phenols such as phenol, alkylphenol, halogenated phenol, alkoxyphenol, and alkoxycarbonylphenol. Specifically, phenol, methylphenol, pn -Butylphenol, p-tert-butylphenol, p-tert-octylphenol, allylphenol, cumylphenol, naphthylphenol, naphthol, bromophenol, tribromophenol, trifluorophenol, methoxyphenol, butoxyphenol, methoxycarbonylphenol, butoxycarbonyl Phenol, dodecyloxycarbonylphenol, octadecyloxycarbonylphenol, and the like. Examples of the compound having a monovalent carboxylic acid derivative structure include carboxylic acid and carboxylic acid chloride, and specifically include acetic acid, acrylic acid, formic acid, propionic acid, propiolic acid, butyric acid, isobutyric acid, methacrylic acid. Acid, palmitic acid, stearic acid, pyruvic acid, acetoacetic acid, glycolic acid, lactic acid, glyceric acid, hexafluoroacetic acid, benzoic acid, naphthoic acid, methylbenzoic acid, butylbenzoic acid, vinylbenzoic acid, pentafluorobenzoic acid, pentabromo Examples thereof include carboxylic acids such as benzoic acid, methyl naphthoic acid and ethyl naphthoic acid, and carboxylic acid chlorides derived from these carboxylic acids.
[0012]
In the case of a transesterification polycarbonate, the ratio of the terminal hydroxy terminal structure can be adjusted usually by adjusting the molar ratio of the starting dihydroxy compound and the carbonic acid diester or by adjusting the degree of vacuum. Further, as a more aggressive method, an adjustment method in which a terminal terminator is added separately during the reaction is also well known. Examples of the terminal terminator used here include monohydric phenols, monocarboxylic acids, and carbonic acid diesters. For example, monohydric phenols and monohydric carboxylic acids having 9 or more carbon atoms are preferably used. P-propylphenol, o-sec-butylphenol, p-tert-butylphenol, cumylphenol, tert-octylphenol, phenylphenol, naphthylphenol, 4-hydroxy-p-quarterphenyl, butylbenzoic acid, octylbenzoic acid , Phenylbenzoic acid, naphthalenecarboxylic acid, and the like. Examples of carbonic acid diesters include carbonic acid diesters derived from monohydric phenols having 9 or more carbon atoms. Butylphenyl carbonate, di (butylphenyl) carbo Over DOO, phenyl cumyl phenyl carbonate, di (nonylphenyl) carbonate, and the like methylphenyl naphthyl phenyl carbonate. In the polycarbonate resin used in the present invention, one kind may be used, or two or more kinds may be mixed and used.
[0013]
The molecular weight of the polycarbonate resin is a viscosity average molecular weight converted from the solution viscosity measured at a temperature of 20 ° C. using methylene chloride as a solvent, preferably 10,000 to 100,000, more preferably 15,000 to 50. , 000.
[0014]
The siloxane compound used in the present invention is an aliphatic or aromatic group having at least one (1) aromatic hydrocarbon group, (2) at least one carboxylate ester bond and / or ether bond on the silicon atom in the structure. It is a polyorganosiloxane formed by bonding an organic group and (3) a phosphorus atom-containing group.
[0015]
Here, the aromatic hydrocarbon group (1) is an aromatic hydrocarbon group having 6 to 50 carbon atoms, such as an aryl group, an alkylaryl group, an arylalkyl group, an alkylarylalkyl group, an arylalkylaryl group, An arylalkyl arylalkyl group etc. are mentioned. For example, examples of the aryl structure include structures derived from aromatic rings such as a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring. Examples of the alkyl structure include methane, ethane, propane, butane, pentane, hexane, heptane, and octane. And a linear or branched structure starting from an alkane. The aromatic hydrocarbon group is represented by a combination of these aryl structures and alkyl structures. Specifically, phenyl group, methylphenyl group, ethylphenyl group, propylphenyl group, butylphenyl group, octylphenyl group, dimethylphenyl group, methylethylphenyl group, diethylphenyl group, dibutylphenyl group, phenylphenyl group, phenyl Methylphenyl group, phenethylphenyl group, cumylphenyl group, naphthyl group, methylnaphthyl group, ethylnaphthyl group, anthracenyl group, methylanthracenyl group, phenanthrenyl group, phenylmethyl group, phenylethyl group, phenylpropyl group, phenylisopropyl group, Examples thereof include a methylphenylethyl group, a naphthylmethyl group, a methylnaphthylethyl group, and a cumylphenylethyl group. These aromatic hydrocarbon groups may be mixed not only in one type but also in two or more types in the molecule. Among these aromatic hydrocarbon groups, a phenyl group, a methylphenyl group, a naphthyl group, a naphthylethyl group, a phenylethyl group, a methylphenylethyl group, and the like are preferable, and a phenyl group, a phenylethyl group are more preferable. Group, naphthyl group, and naphthylethyl group.
[0016]
Furthermore, the organic group of (2) is a group having at least one carboxylate ester bond and / or ether bond in the molecule, and at least one group having a carboxylate ester bond, preferably a group of carboxylate ester And a group having at least one group having an ether bond, preferably a group having a plurality of ether bond groups as a repeating unit, and further having both a carboxylic acid ester bond and an ether bond. Also preferred are groups possessed. For example, -R ¹ -(O-R ¹ ) _m -O (-CO-R ¹ -O) _n -R ² A group represented by -R ¹ -(O-R ¹ ) _m -O (-CO-R ¹ -CO-O-R ¹ -O) _n -R ² A group represented by -R ¹ -O- (R ¹ -O-) _n -R ² A group represented by the formula: ¹ Each independently represents an aromatic hydrocarbon group optionally having an aliphatic hydrocarbon group having 1 to 30 carbon atoms or an aliphatic hydrocarbon group having 6 to 50 carbon atoms as a substituent, and m is 0 to 100. , N represents an integer of 1 to 100. R ² Represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 30 carbon atoms, or an aromatic hydrocarbon group having 6 to 40 carbon atoms. ). Particularly preferably, -R ¹ -(O-R ¹ ) _m -O (-CO-R ¹ -O) _n -R ² A group represented by -R ¹ -O- (R ¹ -O-) _n -R ² The group shown by these is mentioned.
[0017]
R in the formula ¹ Examples of the aliphatic hydrocarbon group having 1 to 30 carbon atoms include alkylidene groups having 1 to 30 carbon atoms. For example, methylene group, ethylene group, propylene group, propylidene group, butylene group, butylidene group, pentylene group, hexylene group, octylene group, decylene group, dodecylene group, octadecylene group, eicosylene group, cyclopentylene group, cyclohexylene group, Examples include a cycloheptylene group, a cyclohexylmethylene group, a cyclohexylethylene group, a cyclohexanedimethylene group, and the like, and may be linear or branched. These aliphatic hydrocarbon groups may be used alone or in combination of two or more. Among these alkylidene groups, a methylene group, an ethylene group, a propylene group, a propylidene group, a butylene group, a butylidene group, and the like are preferable.
[0018]
Moreover, as an aromatic hydrocarbon group which may have an aliphatic hydrocarbon group having 6 to 50 carbon atoms as a substituent, an arylene group includes a phenylene group, a naphthylene group, and the above-described aliphatic group. Examples of the arylalkylidene group include those in which an aryl group such as a phenyl group or a naphthyl group is substituted with the alkylidene group.
Examples of the aliphatic substituent as the substituent include the above-described groups, and these are combinations of those described above with respect to the arylene group.
[0019]
R in the formula ² Examples thereof include those exemplified above as an alkyl group, an aryl group, and an arylalkyl group in addition to a hydrogen atom.
Further, m in the formula is an integer of 0 to 100, but the lower limit is preferably 1 or more, and more preferably 2 or more. The upper limit is preferably 50 or less. Further, n is an integer of 1 to 100, but the lower limit is preferably 1 or more, and more preferably 2 or more. The upper limit is preferably 50 or less.
[0020]
As the phosphorus atom-containing group of (3), a phosphorus atom exists in a structure such as phosphorous acid, phosphorous acid monoester, phosphorous acid diester, phosphoric acid, phosphoric acid monoester, phosphoric acid diester, etc. is there. Specifically, a group represented by the following structural formula (I) is preferable.
[0021]
[Chemical 3]

(Wherein R ^Three Are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 50 carbon atoms, an arylalkyl group, a polyether group, or a polyorganosiloxane group. )
[0022]
R ^Three Examples of the alkyl group, aryl group, and arylalkyl group in the group include those exemplified above, and preferred examples include a methyl group, an ethyl group, a propyl group, a butyl group, and a phenyl group.
The polyether group may be aliphatic or aromatic as long as it is a group derived from a diol or cyclic ether, but is preferably derived from ethylene glycol, ethylene oxide, propylene glycol, or propylene oxide. The number of repeating units is 1 to 100, preferably 2 to 100, and the terminal may be an OH structure or an alkyl ether structure. As a group of polyorganosiloxane, a repeating unit is 3-1000, a preferable minimum is 6, an upper limit is 100, More preferably, it is 50. The polyorganosiloxane group is preferably a polyorganosiloxane group having an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 50 carbon atoms, or an arylalkyl group.
[0023]
The siloxane compound used in the present invention preferably has a structure in which siloxane bonds are linked in a straight chain, but may partially have a branched structure. In the present invention, at least one (1) aromatic hydrocarbon group, (2) carboxylic acid ester bond and / or ether bond as described above is added to the side chain of the linear siloxane compound as described above. Those obtained by bonding an aliphatic or aromatic organic group and (3) a phosphorus atom-containing group are more preferably used.
[0024]
As the linear polyorganosiloxane, M- (W) _n The thing of the structure shown by -M is mentioned.
(M represents a monofunctional structural unit, W represents a bifunctional structural unit, and n represents an integer of 3 to 1,000. W represents an aliphatic structural unit (A), an aromatic structural unit. (B), comprising a structural unit (C) having a carboxylic acid ester bond and / or an ether bond, and a phosphorus atom-containing structural unit (D), and when W is 1, the proportion of each structural unit constituting the W Are A = 0 to 0.6, B = 0.1 to 0.9, C = 0.01 to 0.4, and D = 0.01 to 0.4, respectively.)
[0025]
As a specific example of M, for example,
[0026]
[Formula 4]

(In the formula, each R independently represents an aliphatic hydrocarbon group)
The group of the structure shown by these is mentioned. More specifically, R in the formula is preferably an alkyl group having 1 to 10 carbon atoms. For example,
[0027]
[Chemical formula 5]

[0028]
And the like, but is not limited thereto.
Furthermore, the organosiloxane used in the present invention preferably has a structure represented by the following structural formula (II).
[0029]
[Chemical 6]

[0030]
(In the formula, R represents an aliphatic hydrocarbon group, X represents a hydrogen atom, an aliphatic hydrocarbon group, or an aromatic hydrocarbon group, provided that at least one represents an aromatic hydrocarbon group; Is a hydrogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or an aliphatic or aromatic organic group having at least one carboxylic acid ester bond and / or ether bond, at least one of which is the organic group Z is a hydrogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a phosphorus atom-containing group, provided that at least one is a phosphorus atom-containing group, and further 3 ≦ a + b + c + d ≦ 1000, A represents an integer of 0 or more, and b, c, and d each represents a positive integer.)
[0031]
In the structural formula (II), the M- (W) _n A structure having an aliphatic structural unit (A), an aromatic structural unit (B), a carboxylic acid ester bond and / or an ether bond as a moiety corresponding to the bifunctional group of W in the formula -M The unit (C) and the phosphorus atom-containing structural unit (D) are as follows, and as the polyorganosiloxane used in the present invention, these structural units A to D are each selected from the following compounds: Is preferable. In the following specific examples of each structural unit, the case of only one unit (that is, the case where a, b, c, and d are each 1) is shown.
[0032]
[Chemical 7]

[0033]
Specific example of structural unit A
[0034]
[Chemical 8]

[0035]
Specific example of structural unit B
[0036]
[Chemical 9]

[0037]
Specific example of structural unit C
[0038]
Embedded image

[0039]
Specific examples of structural unit D
[0040]
Embedded image

[0041]
Further, a, b, c, and d in each structural unit indicate the number of the structural units, a is an integer of 0 or more, and b, c, and d are positive integers. Preferably, the lower limit of a + b + c + d is 3, and the upper limit is 1000. When a + b + c + d is less than 3, there are problems such as volatility, which is not preferable. A more preferred lower limit is 6. Moreover, an upper limit becomes like this. Preferably it is 100 or less, More preferably, it is 50 or less. If it is too large, the viscosity will be too high and the handling will be poor. Values in which a, b, c, and d are expressed as a percentage of the total number of bifunctional structural units (W) are expressed as A, B, C, and D, respectively.
The lower limit of A is preferably 0, and the upper limit is preferably 0.6. If A exceeds 0.6, the transparency will be adversely affected.
[0042]
The lower limit of B is preferably 0.1, and the upper limit is preferably 0.9. If B is less than 0.1, there is a problem in transparency, which is not preferable. If it exceeds 0.9, the effect of improving fluidity is inferior. A more preferable lower limit of B is 0.2. A more preferred upper limit is 0.85.
[0043]
The lower limit of C is preferably 0.01, and the upper limit is preferably 0.4. When C is less than 0.01, the transparency is inferior, which is not preferable, and when C is more than 0.4, the heat resistance is inferior. A more preferable lower limit of C is 0.05. A more preferred upper limit is 0.3.
The lower limit of D is preferably 0.01, and the upper limit is preferably 0.4. If D is less than 0.01, the fluidity improving effect is inferior, and if it exceeds 0.4, the heat resistance is inferior, which is not preferable. A preferable lower limit of D is 0.05. A more preferred upper limit is 0.3.
In addition, the ratio of these structural units is siloxane compounds, ¹ It is calculated from the measurement data analyzed by H-NMR and expressed as a molar content (mol / mol).
[0044]
The siloxane compound used in the present invention has the above-described characteristics, and these may be used alone or in combination of two or more.
[0045]
The siloxane compound can be obtained by a known method, and is described in detail, for example, in the Silicone Handbook (Nikkan Kogyo Shimbun (1990)).
Specifically, organochlorosilane is synthesized by a substitution method or a direct method, and further reacted with alcohol or the like to obtain organoalkoxysilane or the like. A siloxane compound is obtained by a condensation reaction using these organochlorosilanes or organoalkoxysilanes. Addition reaction of a compound containing various functional groups such as alkene, alkyne, alcohol, carboxylic acid, phosphoric acid, etc., corresponding to the substituent of the target siloxane compound is carried out on the Si-H group in the siloxane compound thus obtained. Can be obtained. In the addition reaction of the Si—H group, a metal such as platinum, palladium, nickel, rhodium or a compound or complex thereof may be used as a catalyst. Examples of the siloxane compound used in the present invention include a method for producing an organopolysiloxane-polylactone copolymer described in JP-A-6-128380, and a method for producing a phosphorylated polyorganosiloxane described in JP-A-2001-247582. Methods etc. can be applied.
Such a siloxane compound may be obtained from the market.
[0046]
The ratio of the polycarbonate resin and the siloxane compound in the thermoplastic resin composition of the present invention is in the range of 0.001 to 20 parts by weight of the siloxane compound with respect to 100 parts by weight of the polycarbonate resin. If the siloxane compound is less than 0.001 part by weight, the fluidity improving effect is insufficient, and if it exceeds 20 parts by weight, the heat resistance becomes insufficient. The lower limit of the ratio of the siloxane compound is preferably 0.05 parts by weight or more, more preferably 0.1 parts by weight or more. The upper limit of the ratio of the siloxane compound is preferably 10 parts by weight or less, more preferably 5 parts by weight or less.
[0047]
The polycarbonate resin composition of the present invention is excellent in both fluidity and transparency, and is useful when the haze (test piece thickness 3 mm) measured based on JIS K6714 is 10% or less. It is particularly useful when it is 5% or less.
Examples of the method for producing the thermoplastic resin composition of the present invention include a method of blending and kneading by various methods well known to those skilled in the art at an arbitrary stage until immediately before molding the final molded product. Examples of the blending method include a method of mixing with a tumbler, a Henschel mixer, etc., and a method of quantitatively feeding to an extruder hopper with a feeder and mixing. Examples of the kneading method include a kneading method using a single screw extruder, a twin screw extruder or the like.
[0048]
According to the purpose of the thermoplastic resin composition of the present invention, other polymers such as polyester resins, polystyrene resins, polyolefin resins for imparting desired properties, flame retardants, impact resistance improvers, Antioxidant, heat stabilizer, ultraviolet absorber, antistatic agent, plasticizer, mold release agent, lubricant, compatibilizer, foaming agent, glass fiber, glass beads, glass flake, carbon fiber, fibrous magnesium, titanic acid One or more reinforcing agents such as potassium whiskers, ceramic whiskers, mica and talc, fillers, dyes and pigments may be added and contained.
[0049]
The thermoplastic resin composition of the present invention can be formed into a desired molded article according to a conventional molding method such as injection molding or blow molding. As a use of the molded article which consists of the thermoplastic resin composition of this invention, a sheet | seat, a film, miscellaneous goods, household appliance parts, a motor vehicle part, a building material, a hollow container etc. are mentioned, for example.
[0050]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to a following example, unless the summary is exceeded.
The raw materials used in each example are as follows.
(1) Polycarbonate resin: Mitsubishi Engineering Plastics Co., Ltd. Product name: Iupilon S-2000 (viscosity average molecular weight 25,000)
(2) Polycarbonate resin: Mitsubishi Engineering Plastics Co., Ltd. Product name: Iupilon H-3000 (viscosity average molecular weight 19,000)
(3) Polycarbonate resin: Mitsubishi Engineering Plastics Co., Ltd. Product name: Iupilon E-2000 (viscosity average molecular weight 27,000)
(4) Polycarbonate resin: Mitsubishi Engineering Plastics Co., Ltd. Product name: Iupilon H-4000 (viscosity average molecular weight 15,000)
(5) to (19) Siloxane compounds A to N, Q: manufactured by Nippon Unicar Co., Ltd. (described in Table 1 below)
(20) Siloxane compound O: Polydimethylsiloxane: Nippon Unicar Co., Ltd. Product name: L-45
(21) Siloxane compound P: Methyltrimethoxysilane: Nippon Unicar Co., Ltd. Product name: A-163
(22) PCL: Daicel Chemical Industries, Ltd. Product name: Plaxel H1P (polycaprolactone; molecular weight 10,000)
In addition, the ratio of the structural unit in a table | surface calculated from the measurement data which analyzed the siloxane compound by 1H-NMR, and showed it by the molar content rate (mol / mol), and the viscosity showed the measured value in 50 degreeC.
[0051]
[Table 1]

[0052]
In addition, A-1, B-1, B-2, C-1a, C-1b, C-2a, C-2b, C-2c, D-1, D-2 which show the substituent in Table 1 are shown. D-3 shows the following substituents, respectively.
[0053]
Embedded image

[0054]
Embedded image

[0055]
[Examples 1 to 17] [Comparative Examples 1 to 12]
Mixing the polycarbonate resin and the siloxane compound described in the same table or PCL in the ratios shown in Table 2 and Table 3 with a Henschel mixer or tumbler, using a uniaxial vent type extruder of φ65 mm, the barrel temperature Pellets were obtained by extrusion at 270 ° C. The pellets were dried in a hot air dryer at 120 ° C. for 5 hours or more, and then a physical property measurement test piece was injection molded at a resin temperature of 280 ° C. and a mold temperature of 80 ° C. for evaluation. The results are shown in Tables 2 and 3.
[0056]
[Table 2]

[Table 3]

[0057]
[Example 18] [Comparative Example 13]
In the ratio shown in Table 4, when the siloxane compound A shown in the same table was added to the polycarbonate resin (Example 18) and not added (Comparative Example 13), it was formulated with a Henschel mixer or tumbler. The mixture was mixed and extruded at a barrel temperature of 270 ° C. using a uniaxial vent type extruder of φ65 mm to obtain pellets. The pellets were dried in a hot air dryer at 120 ° C. for 5 hours or more, and then a physical property measurement test piece was injection molded at a resin temperature of 280 ° C. and a mold temperature of 80 ° C. for evaluation. The results are shown in Table 4.
[0058]
[Table 4]

[0059]
[Examples 19 to 23]
Polycarbonate, resin, and siloxane compound described in the same table are mixed at a ratio shown in Table 5 by a Henschel mixer or a tumbler, and extruded at a barrel temperature of 270 ° C. using a uniaxial vent type extruder of φ65 mm. Pellets were obtained. The pellets were dried in a hot air dryer at 120 ° C. for 5 hours or more, and then a physical property measurement test piece was injection molded at a resin temperature of 280 ° C. and a mold temperature of 80 ° C. for evaluation. The results are shown in Table 5.
[0060]
[Table 5]

[0061]
The evaluation method in each example is as follows.
Transparency (Haze): Based on JIS K6714, haze was measured using a test piece having a thickness of 3 mm.
Fluidity (Q value) (cc / s): Using a Koka flow tester, a load of 160 kgf / cm ² The outflow amount of the resin at 280 ° C. from a nozzle having a diameter of 1 mm and a length of 10 mm was measured.
Tensile strength (MPa): measured at 23 ° C. based on ASTM D638.
Load deflection temperature (DTUL): Measured at a load of 1.82 MPa based on ASTM D-648.
BF length (mm): 2mm thick bar flow mold, resin temperature 280 ° C, mold temperature 80 ° C, injection pressure 1500kgf / cm ² Molding was performed under the condition of a molding cycle of 45 seconds, and evaluation was made based on the average value of the bar flow length of 15 samples. The larger this value, the better the fluidity.
Impact resistance (Izod impact strength (J / m)): Measured by a notched Izod method using a 3.2 mm thick test piece based on ASTM D256.
[0062]
【The invention's effect】
The thermoplastic resin composition of the present invention has excellent fluidity compared to polycarbonate resin, has a small haze value and excellent transparency, and also has good heat resistance and impact resistance, and transparency. It is useful for various applications that require fluidity, heat resistance and impact resistance.

Claims (9)

(A) In a polycarbonate resin composition comprising 0.001 to 20 parts by weight of (B) siloxane compound with respect to 100 parts by weight of polycarbonate resin, the siloxane compound of component (B) is attached to the silicon atom in the structure. And (1) an aromatic hydrocarbon group, (2) an aliphatic or aromatic organic group having at least one carboxylate ester bond and / or ether bond, and (3) a phosphorus atom-containing group. A polycarbonate resin composition, which is a polyorganosiloxane. The organic group of (2) is —R ¹ — (O—R ¹ ) _m —O (—CO—R ¹ —O) _n —R ² and / or —R ¹ —O— (R ¹ —O—). _n —R ² (wherein R ¹ is each independently an aromatic hydrocarbon group optionally having an aliphatic hydrocarbon group having 1 to 30 carbon atoms or an aliphatic hydrocarbon group having 6 to 50 carbon atoms as a substituent) M represents an integer of 0 to 100, and n represents an integer of 1 to 100. R ² represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 30 carbon atoms, or an aromatic hydrocarbon having 6 to 50 carbon atoms. The polycarbonate resin composition according to claim 1, wherein the polycarbonate resin composition represents a group. The group in which the phosphorus atom-containing group of (3) is derived from at least one kind selected from phosphorous acid, phosphorous acid monoester, phosphorous acid diester, phosphoric acid, phosphoric acid monoester, and phosphoric acid diester The polycarbonate resin composition according to claim 1, wherein the composition is a polycarbonate resin composition. The polycarbonate resin composition according to any one of claims 1 to 3, wherein the phosphorus atom-containing group (3) is a group derived from a phosphate ester. 5. The polycarbonate resin composition according to claim 1, wherein the phosphorus atom-containing group in (3) is at least one of the groups represented by the following general formula (I).

(In the formula, each R ³ independently represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 50 carbon atoms, an arylalkyl group, a polyether group, or a polyorganosiloxane group. .) The polycarbonate resin composition according to any one of claims 1 to 5, wherein the siloxane compound has a structure represented by M- (W) _n -M.
(M represents a monofunctional structural unit, W represents a bifunctional structural unit, and n represents an integer of 3 to 1000. W represents an aliphatic structural unit (A), an aromatic structural unit (B ), A structural unit (C) having a carboxylic acid ester bond and / or an ether bond, and a phosphorus atom-containing structural unit (D). -0.6, B = 0.1-0.9, C = 0.01-0.4, D = 0.01-0.4.) The polycarbonate resin composition according to any one of claims 1 to 6, wherein the siloxane compound is a compound represented by the following general formula (II).

(In the formula, R represents an aliphatic hydrocarbon group, X represents a hydrogen atom, an aliphatic hydrocarbon group, or an aromatic hydrocarbon group, provided that at least one represents an aromatic hydrocarbon group; Is a hydrogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or an aliphatic or aromatic organic group having at least one carboxylic acid ester bond and / or ether bond, at least one of which is the organic group Z is a hydrogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a phosphorus atom-containing group, provided that at least one is a phosphorus atom-containing group, and further 3 ≦ a + b + c + d ≦ 1000, A represents an integer of 0 or more, and b, c, and d each represents a positive integer.) The polycarbonate resin composition according to any one of claims 1 to 7, wherein the siloxane compound has a molecular weight of 800 to 40,000. The polycarbonate resin composition according to any one of claims 1 to 8, wherein a haze (test piece thickness: 3 mm) measured based on JIS K6714 is 10% or less.